Chemistry Reference
In-Depth Information
Neutral
Anion
44
45
44
43
43
42
42
41
41
40
40
FIGURE 9.17
Schematic. molecular. orbital. correlation. diagram. from. the. neutral. to. the.
anionic.ground-state.trimers..The.adding.of.the.extra.electron.is.indicated.by.a.dotted.arrow..
(Reprinted.from.Lopez.Arvizu,.G..et.al.,.
J. Chem. Phys.,
.126(19),.May.21,.194102-1, 2007..
With.permission.)
[128]..The.metal-oxygen.stretching.frequency.is.750.±.20.cm
−1
.for.the.neutral.V
3
O.
and.770.±.20.cm
−1
.for.
V
3
−
..Lower.frequencies.of.415.±.15.cm
−1
.and.340.±.15.cm
−1
.were.
also.found.to.be.active.in.V
3
O..Moreover,.the.V
3
O.spectrum.indicates.that.the.extra.
electron.in.the.anionic.system.occupies.essentially.a.nonbonding.orbital.and.that.the.
neutral.and.anionic.clusters.have.planar.structures.
Motivated.by.this.experimental.work,.we.have.performed.an.all-electron.LCGTO-
KS-DFT.study.of.structural.and.spectroscopic.properties.of.both.neutral.and.anionic.
vanadium.trimer.monoxide.and.neutral,.cationic,.and.anionic.niobium.trimer.mon-
oxide. [183-185].. The. calculated. values. of. the. adiabatic. electron. afinity. and. the.
vibrational. frequencies. were. compared. with. those. recently. measured. [128].. The.
theoretical. study. was. extended. to. the. low-lying. states. of. both. neutral. and. anionic.
vanadium.trimer.monoxides,.and.a.combined.theoretical.and.experimental.approach.
for.the.determination.of.the.V
3
O.and.V
3
O
−
.ground-state.structures.was.presented.
The.same.approach.used.earlier.that.allowed.us.to.simulate.the.ZEKE.spectrum.
and.to.determine.the.ground-state.structure.of.the.V
3
.cluster.[143].was.used.in.order.
to. simulate. the. experimental. negative. ion. photoelectron. spectrum. using. multidi-
mensional. Franck-Condon. factors. calculated. from. the. geometries. and. harmonic.
frequencies.of.the.structures.obtained.for.V
3
O.and.V
3
O
−
..The.comparison.between.
the. experimental. and. theoretical. negative. ion. photoelectron. spectrum. establishes.
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